Manufacture of ethylene urea and the dimethylol derivative thereof



MANUFACTURE OF ETHYLENE UREA AND THE. DllVlETHYLOL DERIVATIVE THEREOFRosser Lee Wayland, .lr., Danville, Va., assignor to Dan River Mills,Incorporated, Danville, Va., a corporation of Virginia No Drawing.Application April 24, 1957 Serial No. 654,645

17 Claims. (Cl. 260309.7)

This invention relates to a process for manufacturing ethylene urea andthe dimethylol derivative thereof. In

United States Patent 2,436,311 there is disclosed a high pressureprocess of reacting ethylene diamine and urea to form ethylene urea. InUnited States Patent 2,517,- 750 there is disclosed a process ofreacting urea and an excess of ethylene diamine to form ethylene urea.In part, the present invention is an improvement on those processes.

This application is a continuation-in-part of allowed patent applicationSerial No. 458,703, filed September 27, 1954, by Rosser Lee Wayland,Jr., now abandoned.

It has now been found that a very satisfactory yield of ethylene ureacan be obtained at atmospheric pressure by reacting substantiallyequimolar quantities of ethylene diamine and urea in the presence of arelatively high boiling point inert fluidizingliquid. In one form of theinvention the fiuidizing liquid is an inert solvent in which bothethylene diamine and urea are soluble. In this form of the invention ithas been found that a water miscible solvent such as a glycol orglycerol is particularly useful in the manufacture of ethylene urea andthe subsequent formation of dimethylol ethylene urea for the treatmentof textiles in an aqueous solution.

In the other form of the invention the fluidizing liquid is a waterimmiscible material such as silicones, parafiin wax, mineral oil andother hydrocarbons having a suit ably high boiling point. Thesefluidizing liquids cannot be termed solvents because a solution of ureain ethylene diamine will not necessarily dissolve in them but some timeswill form separate layers in the absence of stirring or other suitableagitation.

The term relatively high boiling point has a difierent significance inthe two forms of the invention. In the case of a water miscible solventas a fluidizing liquid, any boiling point of 188 C. or above has beenproven satisfactory. In those instances, the boiling point of thesolvent must be such that the boiling point of the reaction mixture inthe final stages of reaction will be about 210 C. or above andpreferably about 230 C., as temperatures in this range are necessary forcompletion of the reaction. Final conversion temperatures vary and arange of from 200 C. to 270 C. has been observed. In those instanceswhere the invention is carried out with a solvent which is immisciblewith the reactants, a somewhat higher boiling point is required. Inthose instances there is little increase in boiling point of thereaction mixture over and above the boiling point of the fiuidizingliquid because there is no true solution and accordingly, thetemperature required for completion of the reaction must be obtainedwithout greatly surpassing the boiling point of the fluidizing liquid.

It has also been found that a somewhat higher temperature is requiredfor completion of the reaction when water immiscible fluidizing liquidsare used. With paraffin wax, for example, ethlyene urea can be formed attemperatures at or above about 245 C.

2,825,732 Fatented Mar. 4, I958 ice The process of the present inventionis characterized by several advantages, as follows:

(1) No high pressure equipment is required, the entire process beingoperable at atmospheric pressure.

(2) No solvent recovery system is needed as it is not necessary to boiloff and recover either fluidizing liquids or excess reactants.

(3) The reaction mixture is kept in a fluid state throughout all stagesof processing. At the time the reaction temperature is in the range ofabout l30-l80 C., an insoluble product is formed, but the fluidizingliquids of this invention keep the insoluble constituents in such astate of dispersion that the fluidity of the mass is not impaired.

(4) No special procedure is necessary for removing. ethylene diamine asthe excess of that material is held to a minimum level which will notinterfere with the use of ethylene urea condensation products which areto be catalyzed in an acid medium.

(5) When the fluidizing liquids are water miscible, they do notinterfere with the use of the ethylene urea in textile treatingmaterials and they have the added advantage of keeping the productliquid at lower temperatures.

In the true solvent operations, considerable saving in solvent cost canbe realized by using the solvent solution of ethylene urea from onebatch as a part of the solvent for the next. It has been foundpreferable to use about 50% fresh solvent for each batch to keep thefreezing point of the final product at a level low enough to permit itto be readily handled in the liquid state.

It will be understood that the water miscible solvents are the preferredfluidizing liquids because they permit operating at a lower temperature,require less stirring and the reaction proceeds more smoothly from aphysical standpoint.

Typical examples of my invention using water miscible solvents are asfollows:

Example 1 30 pounds urea 35 pounds ethylene diamine (86%) 25 poundsethylene'glycol (boiling point 197 C.)

These were heated togethher for about two hours in. a 20-gallon,stainless steel, reaction kettle equipped with a stirrer, refluxcondensers and a thermometer. Ammonia was evolved, and the refluxtemperature rose to l303l5 C. but would rise no higher. At this point,the reaction mixture was an easily stirrable slurry of white, insolublematerial. Distillate was removed until the temperature of the reactionmixture rose to 210- 215 C. (Approximately 2 liters of distillate wascollected.) At this point, the reaction mixture was a clear solutionwhich deposited water soluble crystals of ethylene urea on cooling. Theprecipitated ethylene urea at room temperature was equal to an 87%yield.

To form the dimethylol ethylene urea, 81 pounds of 37% formaldehyde andenough sodium hydroxide to raise the pH to 10 were added to the abovereaction mixture. The temperature rose to about 65 C. and all the solidethylene urea dissolved to give a clear, slightly yellow liquid product.This product was neutralized to pH 7 with hydrochloric acid. The finalproduct was a water-ethylene glycol solution of dimethylol ethyleneurea.

Example 2 The reaction proceededin 'product'on the'fabric'. 7

those 'dimethylol ethylene urea suitable for treatment of textilefabrics.

' e .Eramlz rsi 1.515 and 7 g V The process of Example -1 wasrepeated;using 12S pounds of diethylene glycol (boiling POiHtFZi-S C.) in

' Example'3, dipropylene glycol (boiling-point2'29"1Q.)

in Example 4, glycerol (boiling'pointi2 90? G-) in Exampie 5,thiodiglycol [S(CH CH OH) (boiling pointlfid" C. at reduced pressure,namely, 14 mm.) mum s and the monoethyl etherof diethylene glycol{boiling p ifi 1C-).' x pe In ch instan e he reaction proceeded as inExample =1 with a satisfactoryyield. of ethylene urea and the finalproduct waswaterlsglulq'le andsuitable for treatment ftextilefabrics. Vv lt wi'll bc obvious that'the amount of'inertsolvent is not critical solong as there is enou gh to keep the reaction mixture "stirrajble 1 atall times 'and not too much to lower the boiling point pfth e reactionmixture below the. point 207 at which ethylene ureais formed- 1 Example8 A mixture of ,800 pounds of 98% ethylene diamine (12.4 moles), 785pounds of urea (13.1 moles), 5 50. pounds ota-solution of ethylene ureain ethylene glycol as termed in a previous run in accordance with thisexample (369 pounds of ethylene urea), and 550 pounds of'ethylene glycolwere heated together in a stainless steel reactionkettle equipped with astirrer, thermometer, and. reflux condenser connected to a scrubber toremove amj V monia as it was formed. Ammonia was evolved andthe 7temperature of the reaction mass rose to 4-50 F. (232,

C) over a periodof 12 hours. Solids formed inthe reaction mixture ataxtempe rature of about 320 F. but the fluidity of the 'mass was notimpaired. At tlrecnd of the react-i n eriOd, the product was a clear,slightly yellow liquid which could be cooled to depositionof solidethylene'urea. V

To form the dimethylol ethylene urea, 135(1 pounds of thethusformedethylene urea was reacted with "1804 F. and a pH of 9-10 for'l-Ominutes. then cooled and the pH adjuste d to 7.0-8.0. According tothe PIiDf'fiIt, it would appear thatan The product was excess ofethylene diamine would not adversely affect the p e fi n e n. butj hasnow been foun ma ethylene diamine is difficujlt to remove tron; thesplutjon and thatthe ethylenediam ine interferes with'the .slllise quentprocessing of textiles. for hatreasion, it is portant that no more thanaviary-small excess overone iho ns n es here the reaction pr d ct istdhe sed :f rt e tr atment f textiles. In ne in t nce, a

- textile fabric treated with an ethylene urea fonrnaldehyde lease-tea:7 V

a :npix ure 5.6381335 of 91% i'ethylene'sliamine s ma e), :60 grams of:urea =(1.0:mo'le') and edgrarns 0f n'-decanol (B. P. 231 C.) wereheated together in' a round bottomed flask .eduippedwith .a stirr erthermomreaction proceededas in "Example 9 except that at the .eter andreflux condenser; u the temperature of the mass rose to 2 f C over aperiod Ammonia was evolved and of four hours. Solids formed thereactionmixture.

during the heating cyclebut the mass remained easily tir able throughoutthe re q on pe i d- At the. nd 10 he meannpemarne preductwas a elear,ljghtlyye i--r 0w liq id which d pos e crystals methylene-ulnar I oolig- The product could e ov red fr m ptidn mixture by .eXtraQfiOn Withwater vor by filtration V nd washing of the .filter cake with -a;hYd 0cab0n-so1ven$ and drying. V r

V V :Emmpl 1.0 p The process of Example 9r was repeated using otlgramsof highbo'iling paraflin ,inplaceof the n-decanOl. jflhe end of reactionthe P du nd h p a fi ere pre e as separate layers.

ln operating with some of the fluidizing liquids of this: 7'

invention, .a-slight discoloration of the producthas' b en -noted, Thiscondition has been improved by'tjhe use oi' 2 0? i hout 7 s pounds of37% formaldehyde at a temperature of 160 conditions tending to avoidoxidation. A nitrogen atmosr phe'rleisbneficial' as 'isthe use ofsuitableant oxidants,

Thus it" will beseen that the present invention makes. possiblecommercial manufacture of ethylepeQurca irprii. urea and ethylenediarnine at atmQSpheric pressureijghigh yi by the use of fluid l 1 qii1S hayinglaihigh boiling-point. u I u 11 laim: a s i. The process forproducing ethylene urea which cpm-. 1

piises heating about one mole ofpthylt ne diamine with one-mole of ureaat atmospheric pressure in the presence.

5 ofan organic water miscible solvent whichhas a relatively high boilingpoint of from 189. to 290 .C. and a a t o t e he ing d ent under thereactiqn solidi 'mole of ethylene diamine be used for each. ,r nbleoil-I e?! 7 nd n a i n" PIQdJJCI ill-Which the ethylene urea ys'ils t ney the a tion-of one mole .of use? sndg qnfi m o e hylene diamine P us.a20%v mola cess o ethylene jle did not. show satisfactory wrinklejre,

sistance. (12.7 rnole percent ethylene d iarnineren1ained aftercondensation.) Another portion of the same fabric 1 was treated the samewaywith aujdentical ethylene u1:ea v

'formald'ehyde'condensation product obtained by the re- 7 action of one.rnole .of urea and one mole Qof ethylene diamin'e' plus only 3%molarexcessof ethylene diamine,;;

and that second fabric had'entirely satisfactory wrinkle resistance.(2.1 rnole percent ethylene diamine remained rafter condensation.) Itappears that unreacted ethylene diamine interferes withrcatalysis of thecondensation Shit-able water s.olu ble solvents,in addition to ho ainhe. e ali pl s are the followingi 'tions; W

2. The process ,as set iorth in vent is ethylene glycol. s 7 a s Th P Qas Set fq lhi in 91 1 11 wherein 'tllm 'I- vent is'pro'pylene glycol. v1; i *4. Tha -process. as set forth in claim 1 whereinthewk vent isdiethylene glycol. znto i S t f h}? la in Whereintlie .sgl vent isdipropylene glycol; l

vent is glycerol.

7.2 The 'ar c'ess-as set are in as]; 1 wherein the 3 1-" s nt e nil n lyo -e hy ene,ntearmix yre- The p e s for, re uq hs Wa er-so uble solutioni 7 7 of=d m hy lefl y1ene reaw ii hiccmpris sreacting one fi mole ofethylene diarnine .'.with one p le of urea at atmosphri'cpressure-inthefprese nce of an organic water; 7

miscible solvent which has'a-relafivelyhigh boiling. point ofjrpin about1 89? the other ingredients in derthe reaction? conditions, andthereafter.condensing-the reaction product withfabout two moles offormaldehyde under-basiceonditions.

-91 1 QIQCQSVSI of producing ethylenemrea which com .11 .eaiciehiometric q nti f lre u hr the messa e iioi an m o -at .ci aiinl asthe sol- 1 2-907" 6; and 'ivhich is inert to a tillate until thetemperature of the reaction material rises to about 2lO-2l5 C. andcooling the thus formed product to precipitate ethylene urea.

10. The process for producing ethylene urea which comprises heating at arelatively high temperature below the decomposition point of ethyleneurea about one mole of ethylene diamine with one mole of urea atatmospheric pressure in the presence of an organic fluidizing liquidwhich has a relatively high boiling point of at least 189 C. and whichis inert to the other ingredients under the reaction conditions.

11. The process as set forth in claim 1 wherein said heating is at arelatively high temperature of at least about 210 C. towards the end ofthe reaction and the boiling point of the fluidizing liquid plusreaction components towards the end of the reaction is at least as highas said relatively high temperature.

12. The process for producing ethylene urea which comprises heating at arelatively high temperature below the decomposition point of ethyleneurea about one mole of ethylene diamine with one mole of urea atatmospheric pressure in the presence of an organic fluidizing liquidwhich has a relatively high boiling point of at least about 189 C. andwhich is inert to the other ingredients under the reaction conditions,said heating being at a relatively high temperature of at least about210 C. towards the end of the reaction and the boiling point of thefiuidizing liquid plus reaction components towards the end of thereaction being at least as high as said relatively high temperature.

13. The process for producing ethylene urea which comprises heating at arelatively high temperature below the decomposition point of ethyleneurea about one mole of ethylene diamine with one mole of urea atatmospheric pressure in the presence of an organic water misciblesolvent which has a relatively high boiling point of at least about 189C. and which is inert to the other ingre dients under the reactionconditions.

14. The process for producing water-soluble solutions of dimethylolethylene urea which comprises heating at a relatively high temperaturebelow the decomposition point of ethylene urea one mole of ethylenediamine with one mole of urea at atmospheric pressure in the presence ofan organic water miscible solvent which has a relatively high boilingpoint of at least about 189 C. and which is inert to the otheringredients under the reac tion conditions, and thereafter condensingthe reaction product with about two moles of formaldehyde under basicconditions.

15. The process of producing ethylene urea which comprises heating at arelatively high temperature below the decomposition point of ethyleneurea about one mole of ethylene diamine with one mole of urea atatmospheric pressure in the presence of a water immiscible fiuidizingorganic liquid having a boiling point of at least 231 C. and which isinert to the other ingredients under the reaction conditions.

16. The process as set forth in claim 15 wherein the fiuidizing liquidis molten parafiin wax.

17. The process as set forth in claim 15 wherein the fiuidizing liquidis n-decanol.

References Cited in the file of this patent UNITED STATES PATENTS2,463,311 Larson et a1. Feb. 17, 1948 2,497,308 Larson Feb. 14, 19502,497,309 Larson Feb. 14, 1950 2,504,431 Loder Apr. 18, 1950 2,517,750Wilson Aug. 8, 1950 OTHER REFERENCES Schweitzer, C. 1., Org. Chem, vol.15, page 472 (1950). (Copy in Scientific Library.)

12. THE PROCESS FOR PRODUCING ETHYLENE UREA WHICH COMPRISES HEALTING ATA RELATIVELY HIGH TEMPERAATURE BELOW THE DECOMPOSITION POINT OF ETHYLENEUREA ABOUT ONE MOLE OF ETHYLENE DIAMINE WITH ONE MOLE OF UREA ATATMOSPHERIC PRESSURE IN THE PRESENCE OF AN ORGANIC FLUIDIZING LIQUIDWHICH HAS A RELATIVELY HIGH BOILING POINT OF AT LEAST ABOUT 189*C. ANDWHICH IS INERT TO THE OTHER INGREIDENTS UNDER THE REACTION CONDITIONS,SAID HEATING BEING AAT A RELATIVELY HIGH TEMPERATURE OF AT LEAST ABOUT210*C. TOWARDS THE END OF THE REACTION AND THE BOILING POINT OF THEFLUIDIZING LIQUID PLUS REACTION COMPONENTS TOWARDS THE END OF THEREACTION BEING AT LEAST AS HIGH AS SAID RELATIVELY HIGH TEMPERATURE.